Alkoxynaphthalimido-1,2,4-triazolium salts useful as optical bleaching agents

ABSTRACT

COMPOUND OF THE FORMULA:   2-(B(+)-X-),6-(R-O-)-2,3-DIHYDRO-1H-BENZ(DE)ISOQUINOLINE-   1,3-DIONE A(-)   IN WHICH R IS AN ALKYL RADICAL, OR A HYDROXY, OR ALKOXY SUBSTITUTED ALKYL RADICAL, SAID ALKYL HAVING ONE TO FOUR CARBON ATOMS, X IS A DIRECT LINKAGE OR P-PHENYLENE,B&amp; IS AN N&amp;-(LOWER ALKYL) CYCLOAMMONIUM GROUP IN WHICH THE CYCLOAMMONIUM GROUP IS TRIAZOLIUM CARBON ATOMS TO X THROUGH A CARBON ATOM, THE REMAINING CARBON ATOM IN B&amp; BEING UNSUBSTITUTED OR SUBSTITUTED BY CHLORINE, LOWER ALKYL, PHENYL, OR METHYLTHIO GROUPS, AND A&amp; IS A COLOR MONOVALENT ANION. THESE COMPOUNDS CAN BE USED AS FLUORESCENT BRINGHTENING AGENTS FOR FIBERS BASED ON ACRYLONITRILE POLYMERS OR COPOLYMERS.

United States Patent 3,804,838 ALKOXYNAPHTHALHVIIDO 1,2,4 TRIAZOLIUM SALTS USEFUL AS OPTICAL BLEACI-lING AGENTS Georges Raymond Henry Mingasson, Paris, and Annick Marthe Suzanne Simone Domergue, Eauboune, France, assignors to Ugine Kuhlmann, Paris, France No Drawing. Original application Aug. 9, 1968, Ser. No. 751,349, now Patent No. 3,649,633, dated Mar. 14, 1972. Divided and this application Dec. 1, 1971, Ser. N 0. 203,908

Claims priority, application France, Aug. 11, 1967,

Int. (:1. C07d 55/06 vs. C]. 260-270 R 5 Claims ABSTRACT OF THE DISCLOSU Compound of the formula:

in which R is an alkyl radical, or a hydroxy or alkoxy substituted alkyl radical, said alkyl having one to four carbon atoms, X is a direct linkage or p-phenylene, B is an N -(lower alkyl) cycloammonium group in which the cycloammonium group is triazolium and is attached to X through a carbon atom, the remaining carbon atom in B being unsubstituted or substituted by chlorine, lower alkyl, phenyl, or methylthio groups, and A is a colorless monovalent anion. These compounds can be used as findrescent brightening agents for fibres based on acrylonitrile polymers or copolymers.

This application is a divisional application of copending application Ser. No. 751,349 filed Aug. 9, 1968 (now Pat. No. 3,649,633).

The present invention concerns new optical bleaching agents, their preparation and their applications.

The agents of this invention are novel cationic organic compounds which can be used as fluorescent brightening agents for fibres based on acrylonitrile polymers or copolymers and they are derivatives of naphthalic anhydride corresponding to the general formula:

in which R represents an alkyl radical, B represents a cycloammonium group and A represents a colorless monovalent anion.

The radical R is preferably an alkyl radicalcontaining from 1 to 4 carbon atoms for example, methyl, ethyl, propyl or isopropyl groups. These radicals may be substituted by at least one non-chromophore and non-anionic substituent such as for example a hydroxy or alkoxy group.

By cycloammonium group is meant a monoor polycyclic heterocyclic group containing one or more hetero atoms, the hetero atom or one of the hetero atoms being a quaternary nitrogen atom. Examples of such groups are pyridinium, imidazolium, benzimidazolium, pyrazolium,

' rings may be substituted by at least one non-chromophoreand non-anionic substituent. They may be attachedpyrazolinium, triazolium, thiazolium, benzothiazolium, v

' in which B has the meaning given above. These naphthaloxazolium, isoxazolium, benzo-oxazolium, oxadiazolinm, thiadiazolium, quinolium and indazolium rings. These 3,804,838 Patented Apr. 16, 1974 through a carbon atom to naphthalimido group either by a direct linkage or by a p-phenylene radical.

- The cationic organic compounds of the invention are salts which are soluble in water, and their aqueous solutions show an intense green-blue fluorescence. They have a good afiinity for synthetic fibres based on acrylonitrile polymers or copolymers, with which they form true compounds, the cations being attached at the negative posi-' tions of the fibre. They impact to the acrylic fibres a remarkable effect of whiteness which persists on repeated washing and is stable to light and steaming and fast to chlorine.

Alkoxylated derivatives of naphthalimides are already known. Anslem and Zuckmeyer (Ben, 1899, 32, p. 3291) have prepared 4 methoxy N methylnaphthalir'nide.

Similarly French Pats. Nos. 1,322,849 and 1,344,883 and US. Pat. No. 3,310,564 describe 4-alkoxy-naphthalimides in which the nitrogen atom is substituted by hydrocarbon radicals. These substances are insoluble in water, which makes their application complicated owing to the fact that they have to be very finely dispersed. Those which have a fluorescent brightening action on acrylic fibres owe it to absorption by the fibre, but not to a true' chemical combination with the latter.

The compounds of Formula I can be prepared for example by reacting an alkylating agent of formula A-alkyl wherein A has the meaning given above, for example, an alkyl halide, sulphate or sulphonate, with a compound of the general formula:

. NQBI 06 C O in which R has the meaning given above and B represents a heterocyclic, monoor poly-cyclic group containing one or more atoms of nitrogen or one or more hetero-atoms one of which is a nitrogen atom, possibly in the presence of a solvent such as for example an aromatic hydrocarbon or a chlorinated derivative thereof, an. alcohol or dimethyl formamide. The preferred alkylating agent is an alkyl sulphate such as, for example, methyl sulphate.

- The compounds of Formula II may be obtained for example by any of several known processes, for example, by the condensation of a 4-alkoxy-naphthalic anhydride, and especially 4-methoxy-naphthalic anhydride (C. 1926, II, p. 2817-]. Chem. Soc. 1939, p. 792), with a heterocyclic primary amine of the formula:

'BNH (111) in which B has the meaning given above.

It is alsopossible to prepare the compounds of-Formula II from 4-bromo-naphthalimides of the formula:

imides maybe obtained by condensing 4-bromo-naphthalic 3 anhydride, prepared by the method of Rule and Thompson (J. Chem. Soc., 1937, p. 1764), with an amine of Formula III by a process described by Bradley and Pexton (J. Chem. Soc., 1954, p. 4435). This condensation is pref- 4 140 C. After cooling, the precipitate is filtered ofl, washed with water and dried. 17.4 parts of 4 bromo N (2- pyridyl)-naphthalimide, melting at 247-248 C. are obtained, of the formula:

era-bly carried out in a solpent such as for example water, N alcohol or a hydrocarbon, at a temperature between 100 E N C. and 200 C. Ethylene glycol and diethylene glycol, 0 0 which can be used in a very wide range of temperature, I are particularly suitable solvents. The bromonaphthalimides of Formula IV can then be converted into alkoxynaphthalimides of the Formula II, owing to the mobility of the bromine atom. This property is pointed out by Graebe (Liebigs Ann., 327, p. 87) and by Bradley and t Pexton (J. Chem. Soc., 1954, p. 4434). For this conversion the bromonaphthalimides of Formula IV may :be 5 Example 2 treated in an excess of alcohol ROH at the boilmg point A mixture of 27 parts of 5- 1- 1 under Pressure Wlth an alkah metal alcPholate of 65 parts of 4-bromo-naphthalic anhydride and 500 parts of formula-ROME, 1 which R has the meaning glv above water is boiled under reflux for 5 hours. It is then left and Me lsanalkall metal, Preferably Sodlumto cool, and the precipitate is filtered off, washed with The quaternary saltsof Formula I are very Soluble 20 water and dried. 83 parts of 4-br0mo-N-(3,5-dimethyl-4 water, and their solutions are extremely fluorescent 1n pyrazolylynaphthalimide melting at C are daylight and still more under the influence of ultraviolet tamed, of the formula: rays. They may be applied to fibres based on acrylonltrile CH, polymers or copolymers such as those sold under the C0 trade names Orlon, Courtelle, Crylor, or Dralon, 5 Br-Q Q either by dyeing in a bath having a pH of from 4 to 7 or N-C I by any other process such as for example thermo-fixation Q or incorporation in the mass during spinning. A very C0 small amount of the product, of the order of 0.1 to 0.4% P is sufficient to obtain an excellent whitening effect. 30 On replacing the Z-ammopyndme in Example 1 with The naphthalimides of the Formulae II or IV are new other heterocyclic amines B-NH and operatlng in a compounds but for the most part they have weak fiuosimilar way, the following bromo-naphthalimldes are obrescent properties and an affinity for fibres which is too tained:

M.P., Ex. B'-NH1 Naphthallmides of formula IV C.

3 fi-aminopyri ln 4-bromo-N-(3-pyridyl)-naphthal1m1de 217 4. 2 amin0-6-methylpyrldine 4-bromo-N-(6-methyl-2-pyridyl)-naphthallmide 238 5. 2-aminothiazole. 4-bI'01110-N-(2-thia201y1)manhfhalimidn 293 6. 2-amino-4-methy ole 4-bromo-N-(4-methyl-2-thiazolyl)-naphthalimide 248 7. 2-amino'benzothiazole 4-bromo-N-(Z-benzothiazolyl)naphthalimide 300 8. 6-am1no-2-phenylbenzothlazole. 4-bromo N-(2-phenyl-6benzothiazolyl)-naphthalimlde. 308 9... 4-a.mino-2-phenylbenzothiazole 4-bromo-N-[4-(2-benzothiazolyl)-phenyl]-naphthalimide 326 10.. 2-amln0-bn file 4-bromo-N-(2-benzoxazolyl)-naphthallmide 285 11.. 5-amlno-3-methy" mm "1 4-bromo-N-(3-methyl-5-isoxazolyl)-naphthalimide.-- 295 12 8-am1no2-methylquinollne 4btom0-N-(2-methyl-6-quinolyl)-naphthallmide...-- 287 13 Z-anflno-benzimidazole 4-bromo-N-(2-benzimidazolyl)-naphtha1imide 335 14 6-amlno-l,2d1methyl-benzim1dazol 4-bromo-N-(l,2-dimethyl-6-benzlmidazolyl) -naphthalimlde. 325 15 4'-amlno-2-phenylbenzimidazole. 4-bromo-N-[4-(2-benzim1dazolyl)-phenyl]-naphthalimide 320 16.-. 4'-amlno2-phenyl-l-methyl-benzimidazole 4-bromo-N-[4-(1-methyl-2-benzimidazolyl)-phenyl]-naphthalimide 273 17 fi-amino-lndazole 4-bromo-N-(6-lndazolyl)-naphthal1mide 305 18 3-am1no-6-ehlorolndazole 4-bromo-N-(6-ehloro-3-indazolyl)-naphthalimlde.- 325 19... 2-amlno-5methylthio-thiadiazole-. 4bromo-N-(5-methylthlo-2-thladlazolyl)naphthalimide.. 240 20 -amlno-4-phenylpyrazole 4-bromo-N-(4-phenyl-3-pyrazoly1)-naphthalim1de 298 21 3-am1no-5-phenylpyrazole 4-brom0 N-(5-phenyl-3-pyrazolyl)-naphtha.l1mide 280 22 3-amino-5-methyl-4-phenyl-pyrazol 4-bromo-N-(5-methyl-4-phenyl-3-pyrazolyl)-naphthalimlde... 302 23... 4-amlno-3Fmethyl-5-phenyl-pyrazole.- 4-bromo-N-f3-methyl-5-phenyl-4-pyrazolyl)-naphthalim1de 254 24 4'-amlno-1-phenyHLS-dimethylpyrazole- 4-bromoN- 4-(3,5-dimethyl-1-pyrazoly1)-phenyl]-naphthallm1de 245 25 4'-am.lno-l-phenyl-3,5,5-trimethyl-A2-pyrazollne 4-liigiirgo N-l4-(3,5,5-trlmethyl-1-A2-pyrazo1lnyl)-phenyl]-naphtha1- 238 6. 26 3-amino-1,2,4-4H-trlazole 4-bromo-N-(1,2,4-4H-triazol-3-yl)-naphthalimide 350 27 3-amlno-5-phenyl-1,2,4-4H-triazole. 4-bromo-N-(5-phenyl-1,2,4-4H-triazol-3-yl)-naphthsllmide. 345 28 4-amino-1,2,4-4H-triazole 4-bromo-N-(1,2,4-4H-triazol4yl)-naphtha1imide 350 29.-. 4-arninow'i-phenyl-5-methyl-1,2,4-4H-trlazo 4-bromo-N-[4-(5-methyl-1,2,4-4H-trlazol-3-yl)-phenyl]-naphthallmlde.-- 300 small to have an optical bleaching effect of any interest. In these circumstances it was unexpected that the conversion of the naphthalimides of Formula II into their quaternary derivatives would considerably increase the fluorescence of these compounds.

The following Examples 1 to 61 illustrate the preparation of these intermediate products. Examples 62 to 84 illustrate the preparation of cycloammonium derivatives of naphthalimides according to the invention. Examples 85 and 86 illustrate the use of the cycloammonium derivatives on acrylic fibres. These examples are purely illustrative and the parts given are parts by weight.

NAPHTHALIMIDES OF FORMULA IV Example 1 14 parts of 4-bromo-naphthalic anhydride are condensed with 5.2 parts of Z-aminopyridine in 100 parts of 4 parts of soidum are dissolved in 250 parts by volume of methyl alcohol in an apparatus provided with a stirrer and a reflux condenser. Then 14.12 parts of 4-bromo-N- (2-pyridyl)-naphthalimide are added and the mixture is heated under reflux for 3 hours. The reaction mixture thickens and becomes a pale yellow color. After cooling, the precipitate is filtered off, taken up in dilute acetic acid, filtered and washed with water, then with alcohol. After drying, 11.3 parts of 4-methoxy-N-(2-pyridyl)- naphthalimide of melting point 240 C. are obtained. On recrystallizing from a mixture of alcohol and dimethyl formamide, the product forms long yellow needless melting at 242 C.

By the application of the same process to the 4-bromoethylene glycol by heating the mixture for 5 hours at 130- naphthalimides of Examples 2 to 29, the corresponding 4- ot which are given'belowz- Initial 4- MP. of the bromo-naph- 4-methoxy thalimide of derivative Example ,in C.

l Decomposition.

' Naphthalimides of formula 'M.P-., Ex. B'NH2 11 C.

54-... 2-arnino-benzothiazole..' 4metl'1oxy-N-(2-benzothia- 220 zolyD-naphthalimide. 1 55.... Gamino-Z-phenylbenzo- 4-methoxy-N-(2-phenyl-6- 350 thlazole. benzothiazolyD-naphthalimide. 56...- 2-amino-benzoxazole 4-methoxy-N-(2-benzoxa- 320 ZoI D-naphthamm'de. 57.-.. 6-amino-2-phenylbenzoxa- 4-methoxy-N-(2-phenyl-6- 836 zole. {mengoxazolyD-naphthalm e. 58--.- 6-amino-2-methylquino- 4-methoxy-N-(2-methyl-6- 255 line. quinolyD-naphthalimide. 59-... 2-amino-4-methylquino- 4-meth0xy-N-(4-methyl-2- 262 line. quinolyD-naphthalimide.

Example 60 4 parts of sodium are dissolved in 200 parts by volume of anhydrous ethyl alcohol in a round-bottomed flask provided with a stirrer and a reflux condenser. 14.12 parts of 4-bromo-N-(2-pyridyl)-naphthalimide are added and the mixture is refluxed for 3 hours. After cooling, the precipitate is filtered 01f, washed with a little alcohol, then with water until the filtrate is neutral, and dried. 4-ethoxy-N- (2-pyridyl)-naphthalimide of melting point 232 C. is thus obtained.

Example 61 On replacing the 4-bromo-N-(-2-pyridyl)-naphthalimide in the preceding example by 13.7 parts of 4- bromo-N-(1,2,4-4H-triazol-3-yl)-naphthalimide, 4-ethoxy- N-(1,2,4-4H-triazol-3-yl)-naphthalimide of melting point 338 C. is obtained.

- =NAPHTHALIMIDES 0F FORMULA I Example 62 10 parts of methyl sulphate are introduced into an apparatus provided with a stirrer and a thermometer and are heated to C. and 10 parts of 4-methoxy-N-(2- pyridyl)-naphthalimide are then gradually introduced. The temperature of the mixture is raised to C. and this temperature is maintained for about an hour, until va. sample taken is completely soluble in water. The product is allowed to cool,-diluted with 50 parts of water and'left with stirring to decompose the excess methyl sulphate. It is then boiled with a little decolorizing charcoal and filtered. After cooling, 10 parts of sodium chloride are added to the filtrate, then a dilute solution of zinc chloride, until precipitation is complete. After filtering and drying the precipitate, 12 parts of the chlorozincate of 4'-methoxy-2-naphthalimido-1- methyl-pyridinium monohydrate are obtained. After recrystallizing from water, analysis gives the following figures: I

Calculated for CwHmNzOgCl-I-d/ZZIIClz-i-HgO (percent): C, 51.8; H, 3.86; N, 6.36; CI, 16.1. Found (percent): C, 51.96; H, 3.90; N, 6.70; Cl, 16.7.

This product is in the form of a light beige crystalline powder, and is very soluble in water. Its dilute aqueous solutions show an intense blue fluorescence.

Example 63 5.2 parts of 4-methoxy-N-(2-benzimidazolyl)-naphthalimide are dissolved in 25 parts of dimethyl formamide, 3 parts of methyl sulphate are added and the mixture is heated at 130 C. until a sample is soluble in water. After cooling, 50 parts of water are added, the product is boiled with a little decolorizing charcoal and filtered sodium chloride is added to the filtrate. A light yellow crystalline product is precipitated. 5 parts of 4'- methoxy-Z-naphthalimido 1,3-dimethyl-benzimidazolium chloride are thus obtained. After recrystallizing from water, analysisgives the following results:

Calculated for C H N O Cl, H O (percent): C, 62.06; H, 4.7;.N, 9.87: Found (percent): C, 61.7; H, 5; 'N, 9.49.

This compound gives extremely fluorescent aqueous solutions.

.- 1 Example 64 8 parts of 4-methoxy-N-[4-(3,5-dimethyl-1-pyrazolyl)- phenyl]naphthalimide (Example 47) are heated under reflux in 100 parts by volume of chlorobenzene and 5 parts of methyl sulphate are introduced in a period of an hour. The mixture is boiled for 2 hours and the solvent is removed by steam distillation. The solution is treated with carbon black, filtered, then cooled. The chlorozincate of 4"-methoxy-4-naphthalimido-l-phenyl-2,3,5- trimethyl-pyrazolium is precipitated by the addition of salt and a solution of zinc chloride.

Example 65 3 parts of 4-methoxy-N-(1,2,4-4H-triazol-4-yl)-naphthalimide from Example 51 are gradually introduced into 5 parts of ethyl sulphate heated to 130 C. This temperature is maintained until a sample is soluble in water. The mass is dissolved in water. The solution is boiled with decolorizing charcoal, filtered and sodium chloride and zinc chloride are added to the cooled solution. 4- methoxy-4-naphthalimido-1-ethyl-(or 2-ethyl)-triazolium chlorozincate is thus obtained in the form of a light yellow powder which is soluble in water with an intense blue fluorescence.

Examples 66 to 84 On operating in a similar way according to one of the processes described in Examples 62, 63 and 64 the salts (chlorozincate or methyl sulphate) of other cycloammonium derivatives of Formula I are obtained from 4-alkoxynaphthalimides of Formula II and previously described.

Naphthalimlde o1 Forniilula Ex. Example- Naphthallmlde of Formula I 66. 33 4'-methoxy-2-naphthallmidol,6-dimethylpyrldlnlum (chlorozlncate). 67. 34 4'-methoxy-2-na hthallmldH-methylthiazollum (chlorozlncate 08. a 35 4'-methoxy-2-naphthallmido-3,4-dlmeth ylthlazollum (chlorozlncate). 69. 65 4'-methoxy-fi-naphthallmldo-2phenyl-3-methylbenzothlszolium (chlorozlncate). 70. 59 4'-methoxy-2-naphthallmldo-1,4-dimethylqu1nollum (ehlorozincate). 71 58 4'-methoxy-6-naphthallmido4,2-dimethylquinollum (chlorozincate). 72. 37 4 -methoxy-6-naphtha1imldo-1,2,3-trirnethylbenzlrnldazolium (chlorozincate). 73. 38 4"-methoxy-4-naphthallmido-2-phenyl-l,3-

dimethyl-benzirnidazolium (chlorozlncate). 74. 40 4'-methoxy-6-naphthalimldo-1,2-dimethylindazollum (chlorozlncate). 75. 43 4'-methoxy-3-naphthallrnido-4-phenyl-1,2-

dimethyl-pyrazolium (methyl sulphate). 76. 44 4'-methoxy-3-naphthalimido-S-phenyl-l,2-

dimethyl-pyrazolium (chlorozlncste). 77. 45 4 -1nethoxy-3-naphtha1lmido-4-phenyl-1,2,5-

trlmethyl-pyrazolium (methyl sulphate). 78. 31 4-methoxy-4-naphthallmldo-1,2,3,5-tetramethylpyrazolium (chlorozlncate). 79. 46 4-methoxy-4-naphth allmido--phenyl-1,2,3-

trlmethyl-p azolium (chlorozincate). 80. 47 4-metl1oxy-4 -naphthalimido-l-phenyl-2,3,6-

tn'methyl-pyrazollum (ehlorozincate). I 81. 49 4-methoxy-3-naphthalimldo-1,4 (or 2,4)-dimethyltrlazolium (chlorozincato). 82. 50 4'-methoxy-3-naphthallmldo'5-phenyl-1,4(or 2,4)-

dimethybtrlazollurn (chlorozincate). a 51 4' -n1ethoxy-4-naphthslimldo-1 (or 2) -methyltrlazolium gohlorozinoate). 84.... 52 4-methoxy-4 -naphthalimido-3-phen 1-2,4,5- tlimethyl-trlazollum (chlorozlneattg.

Example 85 A treatment bath is prepared with 3000 parts of water, 3 parts of acetic and 0.4 part of the benzimidazolium salt of Example 63. It is heated to 40-50 C. and 100 parts of an Orlon fabric are introduced. The bath is heated to boiling and maintained at this for an hour. The fabric is removed, rinsed and dried. It has attained a remarkable whiteness. The same effect is obtained on a fabric where the Orlon fibres have been replaced by Courtelle," Crylor or Dralon fibres.

Example 86 The operation is carried out exactly under the conditions described in Example 85, but 5 parts of sodium chlorite have been previously added to the bath. The optical bleaching elfect observed isstill more intense.

We claim: 1. Compound of the formula:

N-x-B A in which R is an alkyl group of one to four carbon atoms, X is a direct linkage or p-phenylene, B83 is an N -(lower alkyl) cycloammonium group in which the cycloammonium group is 1,2,4-triazolium and is attached to X through a carbon atom, the remaining carbon atoms in B being unsubstituted or substituted by lower alkyl or phenyl, and A is a colorless monovalent anion.

2. 4'-methoxy-3-uaphthalimido 2,4-dimethyl-1,2,4-triazolium salts in which the anion is a colorless monovalent anion.

3. 4'-methoxy-3-naphthalimido 5-phenyl-1,4-dimethyl- 1,2,4-triazolium salts in which the anion is a colorless monovalent anion.

4. 4"-methoxy-4-naphthalimido 3-phenyl-2,4,5-trimethyl-1,2,4-triazolium salts in which the anion is a colorless monovalent anion.

5. 4-methoxy3-naphthalimido 1,4-dimethyl-1,2,4-triazolium salts in which the anion is a colorless monovalent anion.

References Cited UNITED STATES PATENTS 3,310,564 3/ 1967 Kasai 260-281 3,330,834 7/1967 Senshu 260-281 3,649,633 3/1972 Mingasson 260-281 3,647,798 3/1972 Klein 260281 OTHER REFERENCES Rice et al.: Jour. Med. Chem., vol. 11, pp. 183-5 (January 1968).

noNAtn o. DAUS, Primary Examiner US. Cl. X.R. 260-281 

